This paper demonstrates the application of near infrared diffuse reflectance spectroscopy (NIR-DRS) measurements as part of digital soil mapping. We also investigate whether calibration functions developed from a spectral library can be used for rapid characterisation of soil properties in the field. Soil samples were collected along 24 toposequences in the Pokolbin irrigation district, ~7 km² of predominantly agricultural land in the Hunter Valley, NSW, Australia. Soil samples at 2 depths: 0–0.10 and 0.40–0.50 m were collected. The soil samples were scanned using NIR under 3 different conditions: field condition, dried unground, and dried ground. A separate spectral library containing soil laboratory measurements was used to develop functions to predict 3 main soil properties from NIR spectra (total C content, clay content, and sum of exchangeable cations). The absorbance spectra were found to be different for the 3 soil conditions. The field spectra appear to have higher absorbance, followed by dried unground samples and then dried ground samples. Although most spectral signatures or peaks were similar for the 3 soil conditions, field samples appear to have higher absorbance, particularly at 1400 nm and 1900 nm. The convex hull of the first 2 principal components of the soil spectra is an easy tool to evaluate the similarity of spectra from a calibration set to an observation. For field prediction, samples need to be calibrated using field samples. Finally, this study shows that NIR-DRS measurement is a useful part of digital soil mapping.